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United States Patent 3,187,021 DIBENZANTHRONE AND ISODIBENZANTHRQNE HAVING SULFATOXYALKYL SULFQNAMIDE GROUPS Kurt Weber, Basel, Switzerland, assignor to Cilia Limited, Basel, Switzerland, a company of Switzerland N0 Drawing. Filed Oct. 10, 1961, Ser. No. 144,051 Claims priority, application Switzerland, flat. 14, 1966, 11,525/6ti 2 Claims. (Cl. 260-354) The present invention provides new vat dyestufifs which contain at least one group of the formula in which A represents an aliphatic radical, advantageously an alkyl radical, in which the group OX is preferably in the ,B-position with respect to the nitrogen atom, R represents an alkyl group or a radical of the formula AOX and X represents an inorganic acyl radical imparting solubility in water, especially a sulfuric acid radical.

The term vat dyestuffs is used herein to denote dyestuffs which are convertible by reduction into a so-called leuco form or vat which has a better afiinity for natural or regenerated cellulose fibers than the unreduced form and in which the original chromophoric system can be restored by oxidation. As suitable vat dyestuffs there may be mentioned especially those of the anthraquinone series, for example, those which contain an unchanged 9: l0-dioxoanthracene ring, and also anthraquinones which also contain fused carbocyclic rings or consist of a plurality of anthraquinone units, and also vat dyestuffs of the perylene tetracarboxylic acid diimide series, the naphthalene tetracarboxylic acid series, the pyrenequinoneor naptho-quinone series and indigoid vat dyestuffs. In addition to at least one hydroxyl group esterified by an inorganic acyl radical, the dyestuffs may contain the substituents usual in vat dyestuffs, such, for example, as halogen atoms or alkoxy, acylamino or arylamino groups. The dyestuffs of the invention are, however, preferably free from nitro or unprotected amino groups. As protected amino groups there may be mentioned those which are in eri-position to a keto group in the anthraquinone ring and which have in ortho-position thereto a carbonyl group or a functionally converted carboxylic acid group, for example, a carboxylic acid ester group or cyano group. As examples of vat dyestuffs which are to contain at least one group of the Formula 1, there may be mentioned: dibenzanthrone, isodibenzanthrone, anthanthrone, dibenzopyrene-quinone, pyranthrone, fiavanthrone, inclanthrone, acedianthrone, N:N-diethyldipyrazole-anthronyl, anthraquinone-Z: l (N)-l':2' (N)naphthacridone, 1:1'-dianthrimidecarbazole, 2:2"-diphenyl anthraquinone 1:2(N)- 5 :7(N)-dithiazole, 124-125- or 1:8-dibenzoylaminoanthraquinone, acylamino-anthraquinones which are obtained by the condensation of two molecular proportions of an (xaminoanthraquinone, for example, l-aminoanthraquinone, 1-amino-4- or l-amino-5-benzoylaminoanthraquinone or aminodibenzanthrone, with a benzene dicarboxylic acid chloride or a dior trichlorotriazine. In addition to the aforesaid dyestuifs of the anthraquinone series, there may be mentioned as representatives of the indigoid vat dyestulfs, indigo or thioindigo and their substitution products and vat dyestuffs of the perylene-tetra-carboxylic acid series or naphthalene tetracarboxylic acid series or pyrenequinone series, or naphtho-quinone series.

The invention also provides a process for the manufacddfifizi Fatented June 1, 1965 ture of the above new dyestufis, wherein (a) a vat dyestuff containing at least one radical of the formula is treated with an agent capable of introducing an inorganie acyl radical imparting solubility in water, or (b) a vat dyestuif containing at least one sulfonic acid halide group is condensed with an amine of the formula 40X HN R in which R, A and X have the meanings given above.

As starting materials for method (a) there are preferably used vat dyestulfs containing one or two groups of the formula .A.1 I'IOH -SOgN in which A, represents an alkylene radical, preferably a methylene radical, A represents a hydrogen atom or an alkyl or hydroxyalkyl radical, preferably containing 1 to 6 carbon atoms, and R represents an alkyl radical or a radical of the formula s Al-CHOH The following groups may be mentioned as examples of radicals of Formula 2:

' The sulfating process may also be carried out with oleum or chlorosulfonic acid or addition compounds thereof with tertiary bases or amides, for instance, pyridine, triethylamine or dimethyl formamide.

As starting materials for embodiment (b) of the process according to the invention there are preferably employed vat dyestuffs containing one or two sulfonic acid halide groups, in particular sulfonic acid chloride groups. These can be obtained by treating vat dyestutfs with chlorosulfonic acid or by reacting vat dyestuffs containing sulfonic acid groups with acid halogenating agents, for example, phosphorus halides, thionyl chloride or chlorosulfonic acid, by known methods. 7

Another method of obtaining the sulfochlorides serving as starting materials comprises acylating vat dyestufis containing amino groups, especially'aminoanthraquinones, with benzoic acid sulfonic acid dichloride, to produce a chlorosulfonyl-benzoylaminoanthraquinone.

The reaction of the said sulfochlori-des with the amine of the formula AOX HN/ V can be carried out in an inert organic solvent, for instance nitr-obenzene, chlorobenzene or ortho-dichlorobenzene, at elevated temperature. However, as the sulfochlorides are generally obtained in aqueous suspension when worked up, it has proved to be advantageous to carry out'the reaction with the amine of Formula 3 in an aqueous medium, advantageously in the presence of acid-binding agents, such. as for example, sodium acetate, sodium hydroxide or sodium carbonate. It is advantageous to choose the molar ratios of the constituents'in such manner that at least one rnol of an amine of Formula 3 is used for one sulfochloride group of the vat dyestuff.

The dyestuffs so obtained can be isolated from the reaction mixture, and, despite the presence of the readily saponifiable grouping of Formula 1, can be worked up into suitable dry dyeing preparations.

dried, if required, after adding extenders having a neutral or weakly alkaline reaction; preferably, the drying is effected at not too high temperatures, if required under reduced pressure.

The new dyestuffs are suitable for dyeing the most diverse materials, 'but more particularly for dyeing or printing on textile materials made of natural or regenerated cellulose by the conventional vat dyeing and printing processes. The colors and prints obtained thereby are distinguished by excellent light fastness and fastness to wetting.

The dyestuifs prepared according to the invention can as a rule be vatted preparatory to dyeing very easily, often at room temperature, even with mild reducing agents such as glucose or. sodium sulphide. They have very good solubility in the vat and excellent levelling and penetrating properties. Especially on regenerated cellulose, strong and very even colorings are obtained which are of the same shade as the corresponding colorings obtained in cotton.

, As the splitting capacity of the acylated hydroxyl groups in the sulfonic acid alkyl amide radical may be somewhat difierent from one case to the other, it is advantageous to adapt the method ofdyeing, that is, especially the concentration of the alkali and of the reducing agent, and also the duration and the temperature during the dyeing or steaming to the dyestutf. The most favourable conditionscan easily be ascertained by means of preliminary tests.

. The following examples, illustrate the invention; the parts, unless otherwise indicated, are parts by weight, the percentages are by Weight, and the temperatures are in degreesv cent-igrade.

Isolation is preferably effected by filtering. The filtered dyestufis may be 4 Example 1 4 parts of the dyestutf of the formula CHz- H-OH OHfCH-OH were added at 0 to 5 C. to parts of concentrated sulfuric acid and dissolved. The solution was carefully poured on to 1000 parts of ice and water and the violet precipitate was filtered off, dissolved in 1000 parts of water at 50 C. 'andexactly neutralized with caustic soda solution. After adding 50 parts of common salt,

filtering was carried out and then drying in vacuo at orig-(i 11-0 s 0 a:

onron-osoan and was well soluble in water, givingta blue-violet color.

solution (70 C.) of 6 parts by volume of caustic soda solution having a specific gravity of 36 B. and 1.2 parts of sodium hydrosulfite in 350 parts of water, 10 parts of cotton were immediately introduced and dyeing was car.- ried out-for 45 minutes at 70 to 80? C. with the addition of 12 parts of sodiumchloride. After dyeing, the cotton was rinsed in cold running water until complete oxidation was obtained and then soaped while boiling. .A strong, reddish blue color having 'good fastness'properties was obtained.

The dyestuff of the Formula 1 can be obtained as follows: 1

11.4 parts of isodibenzanthroneare added at 20 to 25 C. while stirring to 210 parts of chlorosulfonic acid and dissolved. The solution is then heated for 3 hours to 80 to 85" C., cooled to room temperature and carefully poured on to ice. The precipitated sulfochloride is filtered off, washed with a 1ittle ice water and suspended in 500 parts of ice water. 200 parts of diisopropanolamine are added at to C. and the mixture is stirred for 2 hours at O to 5 (3., for hours at room temperature and for 2 hours at to C. The precipitate is then filtered off in the warm state, washed neutral with hot water and dried.

Example 5 parts of the dyestuti of the formula were added at 0-5" C. to parts of sulfuric acid of 96% strength and stirred for 4 hours at this temperature. Working up was carried out as indicated in Example l.

The new dyestuff corresponds as free acid to the formula 0 s im /N S -1| u 0 0 NH ont-crno-soan (O SOs-N OHg-CHgO-S03H It can be used for dyeing as follows:

02 part of the dyestufi was suspended in 50 parts of EOCHzCHg HOCH GH hot water. This suspension was poured into a warm solution (50 C.) of 2 parts by volume of sodium hydroxide solution of 30% strength and 1.2 parts of sodium hydrosul-phite in 350 parts of water, vatting occurring instantaneously. 10 parts of cotton were int-roduced immediately and dyeing was carried out for 45 minutes at 4050 C. with the addition of 12 parts of sodium chloride. The dyeing was followed by oxidai HOCHr-CE; lITH O HOCHfl-CHQ GHEOHQCHZOH CH3 EN EN omomortzon CHQCH-CHOH CHgCHClCH OH 04m N HN CHQCHCICHQOH omcrr-ornou Example 3 The dyestuff of the formula CH CH OH CH CHzOH was used as starting material and the procedure indicated in Example 2 was followedin other respects. The corresponding disulfuric acid ester was likewise obtained and, by the method indicated in Example 2, paragraph 2, likewise dyed, cotton in blue shades having excellent fastness properties.

Example 4 The dyestulf of the formula was employed as starting material and the same procedure as that indicated in Example 2 was otherwise followed. The tetrasulfuric acid ester Was obtained, which, by the dyeing process indicated in Example 2, paragraph 2, dyed cotton in reddish blue shades.

Example 6 3 parts of the dyestufi of the formula CHgCHgOH ornornon CHICH2OH were added at;5 C. to .50 parts of concentrated sulfuric acid and stirred for hours at this temperature. Working upwas carried'out as described in Example 1. The new dyestuff corresponds as free acid to the formula HOaSOCHr-C 9 Golden yellow shades having excellent fastness properties were obtained with this dyestuff by the dyeing process described in Example 2. 1

Example 6 5 parts of the dyestufi of the formula were-added at '20 C. to 80 parts of sulfuric acid of 96% strength and stirred for 5 hours at room temperature. Working up was carried out as described in Example 1. I

.The new dyestufi corresponds as' free, acid to the formula and was soluble in water, giving a yellow color." Yellow 7 shades haying excellent fastness properties were obtained with this dyestufi" by the dyeing process described in Ex ample 2. r

5 The dyestuff of the Formula 5 can be obtained by GH -CH OSOEH CHz-CHgOSOaH qcondens'ation of the condensation product of 2 mols of l-aminoanthraquinone and 1 mol, of cyanuric chloride with 1'- aminobenzene-3-(-N,N-di-fi-hydroxyethyl) sulfonamide in nitrobenzene.

Example 7 5 parts of the dyestufi of the formula were added at 15-20 C. to parts of sulfuric acid of percent strength and stirred for one hour at room temperature. Working up was carried out as described in Example 1. 'l l The new dyestuff of the formula 7 was completelywater-soluble and gives a brown color.

Brown shades were obtained-with this dyest'ufi by the dye- V 75 ing process "described in Example 2. V

9 What is claimed is: 1. A vat dyestuif of the formula Alkyl CH H-OS 03H SO N CHzOH-OSOaH Alkyl 2 alkyl group.

2. The vat dyestuif of the formula CH3 CHx-(JH-OS 03H Sou-N CHrCH-OSOsH References Cited by the Examiner UNITED STATES PATENTS 1,856,207 5/32 Bruns et a1 260-316 2,053,308 9/36 Wuertz 260-353 2,244,655 6/41 Schlichenmaier et a]. 260-303 2,298,533 10/42 Hentrich et a1 260-2495 2,335,698 11/43 Rintelman 260-303 2,368,451 1/45 DAlelio 260-2495 2,567,822 9/51 Moergeli 260-316 2,716,124 8/55 Straley et a1. 260-353 2,735,849 2/56 Ebel et a1 260-249 2,749,352 6/56 Schwechten et a]. 260-3075 2,759,948 8/56 Schwechten 260-3075 2,935,506 5/60 Heslop et a1 260-154 2,985,656 5/61 Weber 260-249 3,022,304 2/62 Staeuble et a1. 260-249 3,029,123 4/62 Putter et a1 260-249 XR 3,043,650 7/62 Wegmann et a1. 8-54.2 3,066,005 11/62 Wedemeyer et a1. 260-249 XR FOREIGN PATENTS 733,471 7/ Great Britain. 1,247,536 10/60 France.

LORRAINE A. WEINBERGER,

Acting Primary Examiner.

IRVING MARCUS, DUVAL MCCUTOHEN, JOHN D. RANDOLPH, LEON ZITVER, Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,187,021 June 1, 1965 Kurt Weber It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 9, lines 30 to 53, for that portion of the formula reading CH2-CH-OSO3H read cH iH-0s0 11 CH CH3 (SEAL) Attest:

ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner of Patents 

1. A VAT DYESTUFF OF THE FORMULA 